Process for the manufacture of phosphate ester derivatives of polyalkylene glycols



United States Patent C) 11 Claims. tri. zen-40s This is acontinuation-in-part application of US. patent application Ser. No.10,564, filed February 24, 1960, and now abandoned.

It is known that polyethylene glycols or addition products thereof canbe esterfied with phosphorus oxygen acids. Due to the differentreactivity of the various hydrogen atoms of the phosphoric acids,however, always partial esterification takes place only so that partialphosphoric acid esters having acid numbers of up to about 10 and whichare liquid or have a low viscosity are obtained.

Now, I have found that novel surface-active products that are suitablefor many purposes are obtained by esterifying, in a manner as suchknown, compounds that contain polyalkylene gylcols and correspond to thegeneral formula with ortho-phosphoric acid, phosphorus oxychloride,phosphorus pentoxide, meta-phosphoric acid, pyrophosphoric acid or anyother polyphosphoric acid formed by further hydrolysis fromortho-phosphoric acid. In this process, the esterification mixture isheated, while continuously discharging the distillation productsliberated, to temperatures in the range of at least 190 and about 280C., preferably 220 and 260 C., until a product is formed which has thedesired degree of condensation and the desired low acid number in therange of about and about 4, preferably 0 and 2. The heating periodrequired can vary within wide limits and depends on the temperatureapplied and, in particular, on the constitution and the cross-linkingability of the compounds of the Formula I used. The heating periodrequired also depends on the quantity of starting compounds used in thereaction mixture as well as on the performance of the reaction withregard to evacuation of the Water formed. In general, heating periodsfrom minutes to about 25 hours are used.

In the general Formula I, R represents hydrogen or an aromatic radicalor a saturated or unsaturated aliphatic or cycloaliphatic radical, nrepresents the integers 2 to 4, in particular 3 or 4, it stands for anintegar from 1 to 10, preferably 1 to 3, v and w represent integers from0 to 10, preferably 0 to 3, x, y and 1 represent integers from 1 toabout 200, in particular 1 to 100, and m m and m stand for integers from0 to about 200, in particular from 0 to 100, the sums of the correlatedintegers x and m y and m and z and m however, not exceeding valuesranging from 1 to about 200. Z Z and Z and which may be equal to ordifferent from each other, represent an oxygen atom or a sulfur atom, orone of the groups in which formlae R represents a preferably lowmolecular saturated alkylene radical, in particular in alkylene radicalthat has 1 to 4 carbon atoms, or a radical of the formula n 2n )m 2 4 )x2 4 wherein m n and x have the meanings given above.

The polyalkylene chains of the compounds of the Formula I may contain,in any desired sequence, butylene oxid and/or propylene oxide members.For the practicability of the reaction it is merely decisive that thepolyalkylene chain terminates with an ethylene glycol member. The term(C I-I O) thus represents an ether chain which contains, once or severaltimes, in any desired sequence, the groups, (3 1-1 0, C H O and C I-I O.

In the compound indicated below, designated as Example l of Formula I,the form modified with propylene glycol thus reads:

As particularly suitable polyalkylene glycols that may be used asstarting materials to carry out the process of the present invention,polybutylene or polypropylene glycols of uniform or mixed compositionare mentioned.

Representatives of this class are:

Referring again to Formula I, R may in particular stand for one of thefollowing radicals:

An aromatic radical containing 1 or 2 benzene nuclei, preferably aphenyl or a naphthyl radical, further phenyl or naphthyl radicals whicheither contain such substituents as are inert towards the esterificationreaction with phosphoric acid, for example, halogen or nitro groups, orwhich are substituted by alkyl radicals that contain 1 to 12 carbonatoms; further, phenyl or naphthyl radicals which are linked by lowmolecular alkylene radicals or by hetero atoms or by such atom groupingsas CO, -S0-, or SO further, saturated or unsaturated, aliphatichydrocarbon radicals which preferably contain 1 to 30 carbon atoms andwhich may also be branched or be substituted by phenyl or naphthylradicals, or such aliphatic hydrocarbon radicals whose chains may beinterrupted by hetero-atoms, in particular oxygen. As such aliphatichydrocarbons there enter into consideration preferably polyalkyleneglycol radicals of the formula in which 111,, n and x have the meaningsgiven above. In said Formula I, R may also stand for a cycloaliphatichydrocarbon radical containing 5 to about 22 carbon atoms, which may bepartially unsaturated and also be substituted by phenyl or alkylradicals containing 1 to 12 carbon atoms. As examples of such compoundsthere are mentioned: cyclohexane, tetrahydronaphthalene,decahydronaphthalene, oi dodecyltetrahydronaphthyl radicals. In case theindices m m and m in the general Formula I are equal to 0, there areconcerned pure polyethylene glycol derivatives of the general formulaThe products obtained by the process of the present invention can beapplied for various technical purposes. Owing to their surface-activity,they are suitable for all purposes for which surface-active substancesare required,

for example, as adhesives, thickening agents in pigment printingprocesses, as sizing agents, finishing agents, emulsion stabilizers,protective colloids, milking fats, flotation agents, emulsifiers,demulsifiers, plasticizers for plastics, and the like. They constituteproducts which are more or less highly viscous and have a consistenceranging from that of ointments or waxes to that of rubber-like productswhich are stringy in the heat, or which upon standing for prolongedperiods at room temperature solidify to wax-like masses of changingopacity.

The decisive features of the process of the present invention are: theapplied high reaction temperature of the esterific-ation mixture, theprolonged reaction period of several hours and the simultaneous andcontinuous complete discharging of the distillation products liberatedfrom the mixture at that temperature. These distillation products whichsubstantially consist of water vapour, are removed either by applying avacuum of at least 15 mm. Hg, or by introducing into the cycle a liquidor gaseous agent which entrains them; this removal is brought about mostsimply with the aid of an inert protective gas, such as nitrogen, carbondioxide, or the like.

If the distillation products are not discharged continuously, the waterthat forms in considerable amounts causes a decomposition of themolecules of the polyethylene glycols or derivatives or additionproducts thereof.

The course which the reaction takes in the process of the presentinvention is not yet completely cleared up. According to our actualknowledge, it is assumed that at the beginning of the reaction thereform at first acid esters of the phosphoric acids mentioned, which,under the action of the liberated water and of the high temperatureapplied are split off at least partially, thereby continuouslyregenerating phosphoric acid which, under the reaction conditions, anewesterifies the hydroxyl groups of the polyethylene glycol chains, sothat, owing to the long reaction periods, the esterification ispractically driven up to the pure tertiary ester. This assumption issupported by the fact that the analysis indicates phosphorus in themolecule of the reaction products and by the low acid numbers asmentioned to be to 2. It may also be possible that in the assumedintermediary ester cleavage some ethylene oxide is separated at the freeends of the polyethylene glycol ether chains from which there mayintermediarily form dioxane.

When assuming, for the purpose of simplification, a monomolecularreaction course, and when using starting substances of the Formula Ia,there is obtained a reaction product corresponding to the followingformula It is less probable that, in the process of the invention, theinitially formed partial phosphoric acid ester is fully hydrolyzed andthat, in addition to the regenerated phosphoric acid in the case of astarting substance of the Formula I, an unsaturated organic compound isformed as intermediary product which corresponds to the general formulaI a (0 2114-0) zCH=CH2]w (III) and which, under dissolution of thedouble bondages lby interlinking or cross-linking with molecules thathave equal constitution, would form condensation products of more orless high molecular weight and consisting of members of the generalformula [Z1(oz11,o)oHCH2] R-[ 2( 2 i- 2-lv tion takes place.

i In the above indicated general formulae, the symbols R, Z Z Z u, v,and w have the meanings given in Formula I.

However, it may also be possible that the reaction to the tertiaryphosphoric acid ester of the general Formula III and the reaction to thephosphorous-free high molecular condensation product of the Formula IVproceed simultaneously and side by side, and that the reaction productsconstitute mixtures of compounds of the Formulae II and IV or mixedproducts from compounds of the Formulae II and IV in varyingproportions.

For the technical effect of the process of the present invention it isof no importance which of these reaction hypotheses is true. This elfectis characterized in that novel products are obtained which may bereproduced and which have valuable properties making them particularlysuitable for a great variety of applications.

In its most general embodiment, the process consists in completelyphosphatizing a starting product of the Formula I or Ia, prepared underthe operational conditions given in any manner desired, at a temperaturein the range of 190 and 260 C., with a prolonged digestion period, whilecontinuously and energetically removing volatile products, such as wateretc. set free by the condensation reactions that are taking place. In apreferred embodiment, the starting material of the Formula I or Ia, froma polyalkylene glycol and an organic compound capable of adding thegrouping is formed in situ and at the same time as the phosphatiza- Theseparate preparation and isolation of the starting product of theFormula I or Ia can thus be dispensed with, and the formation of thisstarting product tbecomes thus an inherent part of the process of theinvention which nevertheless remains a one-stage process and can becarried out in one single reaction vessel.

The starting substance chosen of Formula I or Ia may also be formed insitu in such a manner that the oxalkylation for the formation of thepolyglycolether chains is effected simultaneously with thephosphatization, or that first the phosphatization and thenexthoxylation is effected.

Excess amounts of phosphoric acid can remain in the product as they donot disturb for most of the purposes of application provided for. Ifnecessary, it can be neutralized up to about pH 7 by introducing ammoniaor by adding to the molten reaction mass bases, such as monoethanolamine, propanol amine, methylamine, alkylene oxides, such as ethyleneoxide or propylene-oxide or by adding the reaction product in dry stateat to C. with salts of strong, in particular mineral bases with weakmineral or organic acids, such, for example, as sodium-, potassium-,ammonium-, calciumor magnesium-acetate, sodium-, potassiumorammonium-formate, sodium-, potassiumor ammonium-phosphate as well as thecorresponding carbonates or bioarbonates, or by precipitating thephosphoric acid from the aqueous solutions of the reaction products byneutralization as insoluble salt, for example, calcium phosphate.

The process of the present invention can be carried out at normal,reduced or elevated pressure. Optionally there may be present asentrainer from the cycle an inert liquid which, on the one hand,facilitates the continuous discharging of the volatile lay-products and,on the other, may serve as solvent for the starting material used ineach particular case. As such liquids there enter into consideration:ethylene chloride, tetraline, carbon tetrachloride, benzene, xylene,tetrahydrofurane, further dialkyl glycol ethers or dibutyl ethers andparticularly dioxane.

As representatives of the derivatives of polyalkylene glycol ether ofthe general Formula I which are to be reacted, there are mentioned byway of example:

(A) Pure polyethylene glycols based on ethylene oxide or glycol.

(B) Mixed polyalkylene glycols which contain several units of ethyleneoxide, propylene oxide and/or butylene oxide within their chain andwhich carry one or several etheneoxy groups in terminal position.

The compounds of the groups specified under (A) and (B) may havemolecular weights of up to 5,000. The simplest compound of both 'groupscontains at least 2 etheneoxy groups.

(C) Ethers of the types of compounds specified under (A) and (B) abovewith alcohols or aromatic oxy compounds.

As alcohols, there are mentioned for example: methanol, n-butanol,n-octanol, n-decyl alcohol, lauryl alcohol, stearyl alcohol, melissylalcohol, straight chain aliphatic alcohols such as those obtained by theZiegler process, oleyl alcohol, branched chain alcohols prepared by theoxo-synthesis such as isotridecyl alcohol and isodecyl alcohol, benzylalcohol, cyclohexanol, 1,5-pentanediol, 1,6- hexanediol,1,10-decanediol, 1,12-octadecanediol, 1,2-cyclohexanediol,2,2-di-methylpropane-1,3-diol, glycerine, polyglycerine, pentaerythrite,polypentaerythrite, hexanetriol, .trimethylo lpropane, sorbitol, sugar,starch, as well as the alcohols formed by the reduction of thecarboxylic acids specified hereunder under (G). As aromatic oxycompounds, there may further be used: phenol, ,B-naphthol. pyrocatechol,2,6-dioxy-naphthalene, dioxy-benzophenone, bis-phenols,p-tert.buty1phenol, nonylphenol, 2,6 dichlorophenol, p-nitropheno l,tetrahydro-[i-naphthol, alkylphenol-formaldehyde resins, alizarine. Bytheir formulae there are mentioned:

Semi-ethers formed with alcohols of the general formula 2mm-Uownnom-mmon (D) Monoesters of polyethylene glycols of the generalformula R [COO (C H O -C H OH] formed with organic acids, for example,a( z)14 2 4 )21 z 4 0(C2H4O)14C2H4OH (5) CH CH=CHCH=CHCH COO (C H O -C HOH CH3 C=OH-COO(C2H40)40 C2I14OH CH (E) Products formed by the additionof the compounds of groups (A) and (B) to amines such as aniline,lauryl- N-methylamine, B-naphthylamine, 4,4'-diaminodiphenylmethane.These compounds correspond to the general formulae (CZH4O) x 2H4OH(CQH4O)XCZH4OH and C I-Ig-N or if they are derived from sulfonamides,they correspond to the general formulae otr-rrom-ozn orr a 4 )15O2 4-OH(C2H4O)12C2H4-OH (CZH4O)I2"C2H4OII As phosphatization agents for theesterification of the compounds of the products specified above under(A) to (F) as 'Wfill as those of the specific starting materialsspecified in the preceding paragraph, there are mentioned by Way ofexample: ortho-phosphoric acid, meta-phosphoric acid, pyro-phosphoricacid, polyphosphorus acids derived by dehydration from or-tho-phosphoricacid, phosphorus oxychloride, phosphorus pentoxide.

(G) Carboxylic acids which may be used as an additional esterificationcomponent for the compounds of the groups (A) to (F) in addition to oneof the phosphatization agents specified above, are, for example,undecane acid, lauric acid, myristic acid, pentadecane acid, stearicacid, arachic acid, behenic acid, montanic acid, undecylenic acid, oleicacid, erucic acid, linoleic acid, linolenic acid, adipic acid, azelaicacid, sebacic acid, itaconic acid, citracon-ic acid, dodecylbenzoicacid, nonylnap'hthoic acid, tertbuty-l-phenoxy-acetic acid,butyl-oxyacetic acid, and acids from natural products, for examplericinoleic acid, commercial mixtures of naphthenic acids, resin acids,tall oil fatty acids, linseed oil fatty acid, wood oil fatty acid,coconut oil fatty acid, tallow fatty acid, peanut oil fatty acid, oliveoil fatty acid, fish oil fatty acid, citric acid.

In the above-indicated compounds there may stand for the purepolyethylene glycol chains also mixed polyalkylene glycol chainsaccording to the general Formula I. The polyalkylene chains may thencontain in any desired sequence b-utylene oxide and/or propyleneoxidemembers, however, the chains must always terminate with an ethyleneglycol radical.

The preparation of all polyethylene oxide addition products used asstarting substances in the present process does not form the subjectmatter of the present invention. The starting substances are prepared inknown manner, generally by the action of alkylene oxide in a compoundcontaining a reactive hydrogen atom in the presence of alkali or acidcatalysts, such as potassium hydroxide solution and borontrifluoride, orin some cases by the reaction of compounds containing a reactivehydrogen atom with polyglycol or halogenhydrine.

Of course, there may also the used in the present process severaldifferent compounds of the general Formula I or la in mixture with oneanother, thus offering the possibility of largely varying the finalcondensation products in order to prepare products that have, for anydesired purpose, optimum and specific properties.

The mixed esters of phosphoric acid and carboxylic acid are preparedeither by first phosphatizing a compound of the groups (A) to (F) andthen further esterifying with a carboxylic acid, or by simultaneouslyreacting the compound of the groups (A) to (F) with a carboxylic acidand with a phosphatizing agent.

The condensation products of the groups (A) to (F) have the nature ofmonohydric or polyhydric alcohols, depending on whether they contain intheir molecule one or several polyalkylene glycol chains. The productsthat have the nature of monohydric alcohols yield on reaction with thetrivalent phosphoric acid, tertiary phosphates which are notcross-linked and have defined molecular weights and Which yield aqueoussolutions that have a relatively low viscosity, The products that havethe nature of bior polyhydric alcohols yield on reaction with thetrivalent phosphoric acid, extensively crosslinked products theesterification of which cannot be completed because they become soviscous at 240 C. that they can no more be stirred. They also are notsoluble in water, but only swella ble. In order to be able to completethe esterification of the phosphoric acid, the esterification is carriedout with a quantity of phos phatizing agent smaller than the equivalentquantity, so that free hydroxyl groups are preserved in the finalproduct. It is more advantageous to incorporate in the moleculemonobasic carboxylic acids or ethylene oxide condensation products thathave the nature of monohydric alcohols, which allow a free adjustment ofthe degree of cross-linkage.

As basic components for the novel condensation products that may beprepared in accordance with the process of the present invention, theremay be used, for example:

(1) Alcohols, such for example, as saturated or unsaturated, aliphaticalcohols or polyalcohols containing 1 to about 10' hydroxyl groups and 1to about 20 carbon atoms. As example there are mentioned: glycerin,pentaerythrite, hex-anediol, trimethylol propane, sorbitol, starch,sugar (hexoses, pentoses, etc.), higher fatty alcohols, octadecanediolor thioalcohols,

(2) Aromatic oxy-compounds, such as phenol or napht-hol, as well asderivatives and substitution compounds thereof,

(3) Saturated and unsaturated carboxyiic acids containing 1 to about 30carbon atoms, such as natural or synthetic fatty acids, furtherpolycarboxylic acids containing 2 to 4 carboxyl radicals as well ashydroxycarboxylic acid,

(4) Aliphatic, araliphatic, aromatic or cycloaliphatic amines containing2 to about 20 carbon atoms,

(5) Acid amides that are derived from sulfonic acids or carboxylicacids.

Depending on the type of the basic material chosen, the number andlength of the polyethylene glycol chains present in the molecule and thenumber of free hydroxyl groups that are available for the condensationreaction according to the present invention, the molecular weights andother properties of the products can be varied within wide limits.

Depending on the degree of condensation and the functional groupspresent in addition to the polyethylene chain, the condensation productsprepared according to this invention are in more or less highly viscousform soluble to swellable in Water. They are likewise more or lesssoluble in polar organic solvents, such as chlorinated hydrocarbons,alcohols, esters, ketons and aromates, but they are not soluble innon-polar solvents.

11 The following examples illustrate the invention but they are notintended to limit it thereto:

Example 1 500 grams of polyethylene glycol having a molecular weight of1000 are dissolved in 100 g. of ethylene chloride, 26 g. of POCl areadded dropwise at 80 C. while stirring and the whole is heated underreflux until hydrochloric acid -is no longer split off. After havingdistilled oif the ethylene chloride there are then added 134 g. ofstearic acid and the mixture is slowly heated to 240 C. whilesimultaneously nitrogen is passed through. The water liberated by theesterification and a few organic cleavage products are thereby separatedby distillation. After a reaction of 4-6 hours at 240 C., the moltenmass is discharged. There are obtained in this manner 600 g. of a lightmass which is wax-like and solid in the cold. The reaction product hasan acid number of 2.6.

When the phosphate stear-a'te of the polyglycol intermediarily formed inthis method of operation is not heated over 170 C., its aqueous solutionof strength has at 20 C. a viscosity of 21 centipoises; if, however,this phosphate stearate is further treated thermically in accordancewith the present invention, the reaction product then obtained has in anaqueous solution of 10% strength at 20 C. a viscosity of 47,000 cp.

Example 2 2500 g. of polyglycol having a molecular weight of 1000 areslowly heated under a pressure of mm. Hg on the descending cooler to 240C. with 675 g. of oleic acid and 165 g. of ortho-phosphoric acid of 100%strength, While intensively stirring and this temperature is maintainedfor 5 hours. There are obtained 2800 g. of a soluble reaction productwhich is soluble in water to give a clear solution. The reaction producthas an acid number of 1.5.

Example 3 In accordance with Example 2, 500 g. of polyethylene glycolhaving a molecular weight of 5000 are reacted with 26.8 g. of stearicacid and 6.6 g. of phosphoric acid of 100% strength and there isobtained a condensation product which has in aqueous solution of 5%strength at C. a viscosity of 23,000 op. The reaction product has anacid number of 0.5.

Example 4 Similar to the method of Example 1, 500 g. of polyethyleneglycol having the molecular Weight of 1000 are reacted with 26 g.hosphoroxy chloride to the phosphor semi-ester, 50.5 g. of sebacic acidare then added and the whole is heated while introducing nitrogen at 240C. until condensation takes place. There is obtained in good yield acondensation product in the form of a light, solid, in water clearlysoluble mass that has film-forming properties. The reaction product hasan acid number of 0.7.

Example 5 486 g. of a condensation product of glycerin with 21 moles ofethylene oxide are reacted as described in Example 1 with 142 g. ofstearic acid and 30 g. of orthophosphoric acid of 100% strength. Thereaction product so obtained dissolves in water to clear, viscoussolutions. The reaction product has an acid number of 3.0.

Example 6 474 g. of a condensation product of pentaerythrite with molesof ethylene oxide are reacted in accordance with the method of Example 2with 134 g. of stearic acid and 17 g. of orthophosphoric acid of 100%strength. After about 2 hours, there is formed a very viscous melt whichis difficultly soluble in water. It dissolves in ethylene diglycol andmay then be diluted with water to give a clear solution. The reactionproduct has an acid number of 1.2.

In a manner analogous to that described in the working methods ofExamples 1 to 5, there can be prepared and further processed in thesense of this invention e.g. the phosphoric acid esters of condensationproducts of octadecanediol with 40 moles of ethylene oxide, ofparatoluenesulfonamide with 40 moles of ethylene oxide, of stearyl aminewith 48 moles of ethylene oxide, of pyrocatechol with 20 moles ofethylene oxide, and of aniline with 20 moles of ethylene oxide.

Example 7 342 g. of a condensation product of glycerin with 60 moles ofethylene oxide and 250 g. of polyethylene glycol having a molecularweight of 2000 are dissolved in g. of ethylene chloride, 20 g. ofphosphoroxychloride are added, the Whole is boiled on the reflux cooleruntil the cleavage of hydrochloric acid ceases, the solvent is removedby distillation, 67 g. of stearic acid is added, the whole is thenslowly heated to 240 C., while carbon dioxide -is passed through, andsaid temperature is maintained for 2 to 4 hours until the reactionmixture becomes viscous. The aqueous solution of 5% strength of thereaction product that has solidified to a wax-like mass has at 20 C. aviscosity of 36,500 cp. The reaction product has an acid number of 2.0.

Example 8 In accordance with the process employed in Example 7, 333 g.of polyethylene glycol having a molecular weight of 1000 and 214 g. of acondensation product of stearyl alcohol with 8.8 moles of ethylene oxideare reacted with 51 g. of phosphoroxychloride and the whole is treatedin the manner described. There is obtained a clear melt having apetroleum jelly-like consistency, and which has at 20 C. in aqueoussolution of 10% strength a viscosity of 38,200 op. The reaction producthas the acid number 0.3.

Example 9 In the same manner as described in Example 7, a mixture 'of342 g. of a condensation product of (glycerin with 60 moles of ethyleneoxide and 250 g. of polyethylene glycol having a molecular weight of1000 is partially esterified with 19.5 g. of phosphoroxychloride, 67 g.of stearic acid is then added and the mixture is then held for 5 hoursat 240 C. while passing through a stream of nitrogen. There is obtaineda condensation product which in an aqueous solution of 10% strength hasa viscosity of 156,000 cp. at 20 C. The reaction product has an acidnumber of 1.8.

Example 10 500 g. of polyethylene having a molecular weight of 1000 areslowly heated under a pressure of 15 mm. Hg to 240 C. with 134 g. ofstearic acid and 33 g. of orthophosphoric acid and held at thistemperature for six hours. After having cooled, there is obtained aWax-like condensation product which exhibits in an aqueous solution of10% strength and at 20 C. a viscosity of 7850 cp. The reaction producthas an acid number of 1.3.

When in this formulation the ortho-phosphoric acid is replaced by thesame amount of pyrophosphoric acid or rnetaphosphoric acid, there areobtained condensation products the aqueous solutions of 10% strength ofwhich exhibit at 20 C. a viscosity of 1670 cp.

Example 11 488 g. of propylene glycol-oxethylate from 30% propyleneoxide and 70% ethylene oxide, molecular weight 4880, are dissolved in200 g. of ethylene chloride, and reacted with 10.2 g. of POCl and, afterhaving removed the solvent by distillation, heated for 5 hours to 240 C.While passing through a stream of nitrogen. The reaction product is aclear aqueous solution, the viscosity of which 1.3 is stronglyincreasing while raising the temperature. The reaction product has anacid number of 1.6.

Example 12 103.6 g. of phosphoxychloride are added dropwise Whilestirring to 600 parts by Weight of polyethylene glycol, molecular weightof 600, and the whole is heated to 90 C. As soon as the strong evolutionof hydrochloric acid has terminated, the whole is slowly heated on adescending cooler to 240 C. After having stirred for about 2 hours atthis temperature, during which time about 100 parts by Weight of easilyvolatile components are removed by distillation, the reaction massbecomes thick and viscous. It is highly viscous, stringy, elastic,slightly yellow, and solidifies after having been allowed to stand forseveral hours at room temperature to form a turbid Wax. Yield: 560 partsby Weight (including phosphoric acid).

Example 13 In the same manner as in Example 12, 600 parts by Weight ofpolyethylene glycol of a molecular weight of 600, are reacted with 48parts by weight of phosphorus pentoxide. The condensation product isformed by heating to 230-240 C. and resembles to that of Example 1.

Example 14 400 parts by Weight of polyethylene glycol of a molecularweight of 800, and 33 parts by Weight of orthophosphoric acid of 100%strength are cycled out with 100 parts of tetraline up to 220 C. About17 parts by volume of a liquid that is insoluble in Tetralin are therebyseparated in the Water trap, Whereas the reaction mass becomesincreasingly more viscous. The condensation having progressed to thedesired degree, the Tetralin is removed by distillation under reducedpressure. There is obtained a condensation product that has similarproperties as those of the products of Examples 1 and 2.

Example 15 600 parts by Weight of polyethylene glycol of a molecularweight of 3000, and 13 parts by Weight of orthophosphoric acid of 100%strength are heated on an appropriate heating bath to 240 C. whilecontinuously separating by distillation under reduced pressure (15 mm.Hg) an easily volatile liquid until a viscous melt is formed. There areobtained 593 parts by weight of a transparent, rubberlike tough viscous,yellowish-brown mass, which solidifies upon standing at room temperaturefor several hours to a slightly opaque hard wax.

Example 16 1000 parts by weight of polyethylene glycol, molecular weight1000, and 66 parts by weight of orthophosphoric acid of 100% strengthare heated on the heating bath, While Well stirring and at a pressure of12 mm. Hg, within 2 hours to 240 C. With a distillation .loss of 36parts by weight, there are obtained 994 parts by Weight of acondensation product.

Example 17 500 g. of polyethylene glycol (2000)-semi-phosphate having anacid number of 10.2, prepared by heating about 500 g. of polyethyleneglycol having a molecular weight of 2000 with 13 g. ofphosphoroxy-chloride, are heated to 240 C. While passing through 55l./hour of nitrogen. After a reaction period of hours there is obtaineda product having an acid numberof 1.3.

390 g. of this product are heated with 52 g. of stearic acid for 8 hoursto 240 C. while passing through 50 l./ h. of nitrogen. The acid numberof the reaction product is 4.2. Upon determination of the viscosity, anaqueous solution of the product of strength in a Ford viscosimeter withnozzle 8 and 25 C. shows a passage time of 18 minutes and 32 seconds.

14 Example 18 500 g. of polyethylene glycol having a molecular weight of2000 are heated for 5 hours to 240 C. together with 67 g. of stearicacid and 8.25 g. of phosphoric acid while passing through nitrogen.

In the reaction, a distillation loss of 19 g. of organic substance and 4g. of water occurs. The acid number of the reaction product amounts to3.3. The product is a yellowish solid wax, the aqueous solution of 10%strength of which exhibits in the Ford viscosimeter With nozzle 8 apassage period of 12 minutes and 5 seconds.

Example 19 705 g. of the product of the condensation of a p-sec.-butylphenol-formaldehyde resin with 60 mols of ethylene oxide per weightequivalent of resin, in the presence of an acid catalyst, are treatedfor 2 hours to 240 C. with 17 g. of orthophosphoric acid of strengthwhile passing through a stream of nitrogen. The viscosity of the melt israpidly increased While the acid number falls to 2.

The reaction product is a hard wax which yields highly viscous aqueoussolutions.

Example 20 500 g. of polyethylene glycol having a molecular weight of2,000 are reacted with g. of the product of the condensation oftri-sec.-butylphenol with 10 mols of ethylene oxide, and with 38.5 g. ofphosphorus oxychloride according to the method described in Example 19,until after 6 hours the acid number falls to 2.5.

The reaction product constitutes a light, semi-solid mass which isclearly soluble in water and exhibits marked surface-active properties.

A 20% aqueous solution thereof shows in a DIN cup with the nozzle 4 at25 C. a passage time of 7 minutes and 30 seconds.

Example 21 ,590 g. of a condensation product of octadecanediol with 60mols of ethylene oxide are heated for 6 hours to 240 C., while passingthrough nitrogen, with (a) 5.2 g. of ortho-phosphoric acid (85%strength) corresponding to 1/ 3 equivalent,

(b) 7.75 g. of ortho-phosphoric acid (85% strength) corresponding to 1/2 equivalent,

(0) 10.4 g. of ortho-phosphoric acid (85% strength) corresponding to 2/3 equivalent,

(d) 15.5 g. of ortho-phosphoric acid (85 strength) corresponding to 3/3equivalent.

In the case of (a), (b) and (c), the bright wax-like reaction productsobtained have an acid number of 0, while (0) has an acid number of 2.9.

The viscosities of aqueous solutions of 10% strength at 20 C. are:

Cp. Starting material 12.4 Product obtained according to (a) 101.6Product obtained according to (b) 625 Product obtained according to (c)26,780

The product obtained according to (d) is only swellable in water.

I claim:

1. A process for the manufacture of surface-active polyalkylene-glycolderivatives, comprising esterifying a compound of the formula 15 whereinIt stands for the integers 3 or 4, u stands for an integer from 1 to 10,v and w represent integers from to 10, x, y and z represent values from1 to 200, m m and m represent values from 0 to 200, the sum of thevalues of the correlated integers x and 111,, y and m and z and m, notexceeding in each case values ranging from 1 to 200, Z Z and Z representa member selected from the group consisting of oxygen, sulfur, -COO,CONR SONR SO and -O wherein R stands for a member selected from thegroup consisting of a lower alkylene radical and a radical of theformula n 2n )m 2 4 )x 2 4 wherein m n and x have the meaning givenabove and R stands for a radical selected from the group consisting ofphenyl, hydrogen, naphthyl, substituted phenyl or naphthyl wherein thesubstituents are chloro, nitro or alkyl having up to 12 carbon atoms,phenyl or naphthyl linked by lower alkylene, CO-, SO or SO alkyl havingup to 30 carbon atoms, phenyl substituted alkyl having up to 30 carbonatoms in the alkyl, naphthyl substituted alkyl having up to 30 carbonatoms in the alkyl, alkyl containing up to 30 carbon atoms having oxygenin its chain, hydrocarbylcycloaliphatic having from 5 to 22 carbonatoms, phenyl substituted hydrocarbylcycloaliphatic having from 5 to 22carbon atoms, alkyl substituted hydrocarbylcycloaliphatic having from 5to 34 carbon atoms or a radical of the formula wherein m n and x havethe meaning defined above, by heating to 190 to 280 C. for 5 minutes to2,5 hours with a member selected from the group consisting oforthophosphoric acid, phosphorus oxy chloride, phosphorus pentoxide,metaphosphoric acid, pyrophosphoric acid, and a polyphosphorus acidformed by further dehydration from ortho-phosphoric acid, andcontinuously and simultaneously removing volatile by-products liberatedduring the reaction to form a product having the acid number within therange of 0 to 4.

2. A process as claimed in claim 1, in which a polyethylene glycol of amolecular weight from 600 to 5,000 is simultaneously reacted with analiphatic mono-basic to tetrabasic acid with 6 to 30 carbon atoms and aphosphorylating agent selected from the group consisting ofortho-phosphoric acid, phosphorus oxychloride, phosphorus pentoxide,meta-phosphoric acid, pyrophosphoric acid and polyphosphorus acidsderived by dehydration from ortho-phosphoric acid.

3. The process as claimed in claim 2 in which during the reaction acontinuous stream of nitrogen is passed through the reaction mixture.

4. A process as claimed in claim 1, in which a condensation product ofpropylene oxide and ethylene oxide with a molecular Weight of up toabout 5,000 is phosphorylated with an agent of the group consisting oforthophosphoric acid, phosphorus oxychloride, phosphorus pentoxide,meta-phosphoric acid, pyrophosphoric acid and polyphosphorus acidsderived by dehydration from ortho-phosphoric acid, while passing astream of nitrogen through the reaction mixture and continuouslyremoving volatile by-products liberated in the reaction until a productis formed, the acid number of which ranges from 0 to 4.

5. The process as claimed in claim 1 wherein the reaction is carried outunder reduced pressure.

6. The process as claimed in claim 1 wherein an inert gas is passedthrough the reaction mass.

7. The process as claimed in claim 1 wherein an inert solvent is addedto the reaction mass.

8. The process for the manufacture of surface-active polyalkylene glycolderivatives according to claim 1 in which the compound Of said generalformula is formed in situ during phosphatization by oxethylating acompound of the formula z (C..I-I2nO)m and wherein R, Z Z Z n and m havethe same meaning as defined in claim 1.

9. A process as claimed in claim 1, in which a polyalkylene glycol witha molecular weight from 600 to 5,000 is separately reacted in two stepswith an aliphatic mono-basic to tetrabasic acid with 6 to 30 carbonatoms and a phosphorylating agent selected from the group consisting ofortho-phosphoric acid, phosphorus oxychloride, phosphorus pentoxide,metaphosphoric acid, pyrophosphoric acid and polyphosphorus acidsderived by dehydration from ortho-phosphoric acid, while continuouslypassing a stream of nitrogen through the reaction mixture, the sequenceof both steps being chosen ad libitum.

10. The process according to claim 1 wherein the reaction is carried outin an inert liquid serving as an entrainer for the volatile by-productsfrom the cycle and selected from the group consisting of ethylenechloride, tetraline, carbon tetrachloride, benzene, Xylene,tetrahydrofurane, dialkyl glycol ethers, dibutyl ethers, and dioxane.

11. A process for the manufacture of surface active derivatives ofpolyalkylene glycols, in which a compound selected from the groupconsisting of polyethylene glycols; mixed polyalkylene glycolscontaining a plurality of units of a member selected from the groupconsisting of ethylene oxide, propylene oxide, butylene oxide andmixtures thereof, and carrying at least one ethylene oxide group interminal position and having molecular weights from 88 up to 5000;ethers of said polyethylene glycols and of said mixed polyalkyleneglycols with a member se lected from the group consisting of aliphaticalcohols containing up to 10 hydroxy groups and up to 20 carbon atoms,phenyl and naphthyl alcohols, substituted phenyl and naphthyl alcoholswherein the substituents are alkyl, nitro or chloro and formaldehydederivatives of said phenyl and naphthyl alcohols; esters of saidpolyalkylene glycols and of said mixed polyalkylene glycols with amember selected from the group consisting of alkyl carboxylic acidscontaining 8 to 30 carbon atoms and alkyl polycarboxylic acidscontaining 2 to 4 carboxy radicals and products of said polyalkyleneglycols and of said mixed polyalkylene glycols formed by addition withacid amides derived from a member selected from the group consisting ofsulfonic acids and carboxylic acids, is reacted at a temperature betweento 280 C. for a period of five minutes to 25 hours with a memberselected from the group consisting of ortho phosphoric acid, phosphorusoxychloride, phosphorous pentoxide, metaphosphoric acid, pyrophosphoricacid and polyphosphorous acids formed by further dehydration fromorthophosphoric acids while continuously and simultaneously removingvolatile by-products liberated during the reaction, until a producthaving an acid number within the range of 0 to 4 is formed.

References Cited by the Examiner UNITED STATES PATENTS 1,917,251 7/ 1933Harris 260403 2,026,785 1/ 1936 Harris 260403 2,133,690 10/1938 Epsteinet al. 260403 2,243,868 6/ 1941 Katzman 260403 2,643,261 6/1953 Matuszaket al 260403 2,712,511 7/1955 Orozco et a1. 260461 2,755,296 7/ 1956Kirkpatrick 260403 3,004,056 10/1961 Nunn et al. 260-403 3,004,05710/1961 Nunn 260403 CHARLES B. PARKER, Primary Examiner.

DANIEL D. HORWITZ, ANTON H. SUTTO,

Assistant Examiners.

1. A PROCESS FOR THE MANUFACTURE OF SURFACE-ACTIVE POLYALKYLENE-GLYCOLDERIVATIVES, COMPRISING ESTERIFYING A COMPOUND OF THE FORMULA